Extraction of beryllium from ores



F 17 1942- H. H. ARMSTRONG EXTRCTION OF BERYLLIUM FROM CRES Filed Aug. 23, 1937 MNO EDTTTFEN@ Patented Feb. 17, 1942 UNITED STATES PATENT .OFFICE EX'IEAJ'.I'IONl 0F FROM GRES Harry Howard Armstrong, Newport, Pa. Application August 23, 1937, Serial No. 160,558

(Cl. 'l5-150) 3 claims. This invention relates to the extraction ot metals from ores, more particularly to the recovery of beryllium and beryllium compounds from beryllium-containing minerals. and the utilization of the recovered beryllium in the metallurgical elds. l

In the past it has been suggested to utilize beryllium metal as an alloying constituent i-n ferrous `and non-ferrous alloys. found that the addition of minor percentages of beryllium to metals, such as aluminum, copper,

nickel and iron, very markedly improves the.

physical and chemical characteristics of the alloy.

Despite the marked value of beryllium as an .alloying constituent, the amounts which have been employed in the metallurgical iield are very small. This, as is known, is due to two factors. In the first place', as compared .to most other alloying metals, the beryllium ores, such as beryl, may be considered to be relatively rare. In the second place, and more importantly, the methods of extraction which have been proposed and used heretofore are complicated and expensive. The typical method of extracting beryllium metal from a beryllium-containing ore, such as beryl, comprises essentially an electrolytic recovery treatment by deposition of the beryllium from a fused fluoride bath. The operation is lengthy, complicated and expensive, involving the use of very high temperatures and relatively' expensive fluxes, and the like.

For these reasons the potential value of Aberyllium as an alloying constituent has not, to any great extent, been availed of. -Beryllium metal is still very expensive and altogether too expena sive to be employed in any considerable amounts in structural materials. Some beryllium metal has been used commercially in combination with copper to produce a copper-beryllium alloy of exceptional valuable characteristics. This alloy is of peculiar utility in the electrical elds but the extent of its use is `very materially limited because of the very high cost oi the alloy, which is due largely to the great expense of beryllium metal.

Ifberyllium metal or beryllium compounds,

- amenable to employment in typical metallurgical processes,

could be produced at a relatively low cost, aV wide range of valuable alloys would be made available to the industries at a reasonable The present invention deals broadly with this problem. In a broad aspect the invention comprehends the concept yof cheaply extracting It has been beryllium, or beryllium compounds, from beryllium-containing minerals. The invention further contemplates the concept of associating the extracted beryllium or beryllium compounds with other metals, such -as iron, nickel, and the like,

or compounds of these metals, so as to 'produce what, for the sake of a term, may becalled master alloys; that is to say, concentrates of beryllium, or compounds thereof, with othermetals, or compounds thereof, which concentrate is available for employment in typical'metallurgical processes so as to produce ultimate allbys of any desired percentage composition. A 4 Y With this concept in mind, it will be appreciated that, given a cheap method of extraction of beryllium or beryllium compounds, 'and given such a method in which other metallic elements may be associated with the beryllium during the course of treatment, then the possibility is immediately established of producing beryllium, or beryllium compounds, or concentrates of beryllium or beryllium compounds, with other metallic constituents, so asto provide an alloying concentrate immediatelyavailable for. employment in the standard metallurgical processes in c sired percentage composition.

' Yet another object is to providefa method of extracting beryllium from beryllium-containing ores, in which extraction other valuableztrnetallic constituents may be intimately and advantageously associated with the beryllium to produce a concentrate of beryllium and such metallic metal.

constituents.

Yet a further object of the invention is -to provide improved vmethods of alloying beryllium with ferrous and nonf-ferrous metals.

A still further object is to produce new and improved beryllium-containing alloys.

As indicated hereinbefore, the usual method .now employed, of producing beryllium alloys, is

torst produce the substantially pure beryllium electrolytic. high temperature treatment. Another method which has been suggested' in the This involves, asl noted. an expensive Carbides of an alkali as those of nickel,

or non-ferrous melts so as to produce; a master alloy or'an ultimate alloy of the desired composition. Y

In o ne methodA of procedure Aunder the invention, beryllium carbide, if desired, in association with other metal carbides, 'is produced directly .from the ores and the beryllium carbide or other used directly in the promixed metal carbides duction of alloys. 'As -a typical example of such bide may be produced from typical beryl, analyzing about 70 per cent. SiOz, 16 per cent. A1203, 13 per cent. BeO, and 1 per cent. FeO. `In carrying out the process, the ore is rst pulverized to a desired state of subdivision and is then mixed and briquetted with carbon or with a carbide.

metal such as calcium, magnesium, and the like,may be employed. The briquetted mixture is then treated in a furnace, preferably an electric arc furnace, and heated to temperatures suiciently high to volatilize the silica. f 'I'he volatilized silica maybe withdrawn from the heating zone or furnace and passed to a silica recovery plant. Under the high temperatures employed, the beryllium and aluminum contents-of the ore are converted tothe respective carbides, i. e., Be4C3 and A1403. In the preliminary preparation of the mixture which is to be treated in the furnace, any suitable briquetting or binding agent may be employed. .In these circumstances, that is to say, by employing such a mixture of beryl and carbon, or carbides, the silica is distilled and the fused residue is comprised of a' mixture of beryllium and aluminum carbides, together with a small amount of impurities such as iron silicide.

, This mixture may be employed directly to reduce metal salts or compounds such, for example, iron, chromium, beryllium and the like vto produce a master alloy of these metal values.

In another method the product so produced (i.

e. the beryllium carbide composite) is preferably pulverized or ground and is treated with a strong mineral acid under heat and pressure to produce the corresponding salts of the metals in the cake. For example, in one preferred mode of operation, thecarbidev mixture is admitted to a digester and digested upder heat,

v is to undergoldigestion.. For example, to lthe dry pulverized mass oi the carbides, fproduced in the rst step, there may be added metals such as nickel, molybdenum, and the like, or salts of ultimate production of and the autogenous pressure developed` with strong sulphuric acid of approxthese circumstances, substana process, beryllium carbide and aluminum carthese or other metals which are desired in the ultimate fabricated alloy.

During the digestion operation, as will be appreciated, certain hydrocarbon gas may be produced, the particular type of vgas depending on the character of the material undergoing digestion; for example, as is known, under the thermal conditions obtaining lduring the digestion stage, acetylene may be produced when the starting material contains calcium carbide. Similarly, in the pressure digestion, methane is produced from aluminum carbide as well as the beryllium carbide. During the pressure digestion step, therefore, such gases may be withdrawn from the pressure vessel, in any suitable manner, andpassed to a gas holder. Such gas may, if desired,

be4 utilized as a heating medium in the plant, I

or asmore particularly described later, as a reducing agent in the step alloys.

The dry cake produced as a result of the pressure .digestion may then be leached Kto take in solution the soluble metal sulphates. The excess of producing the master carbon may be filtered from the solution and the solution then treated to separately or conjointly recover the metal values thereof. For example, the metal values may be precipitated from the solution with caustic soda or potash.

An excess of caustic may be employed so as to preferentially precipitate the iron and beryllium While maintaining the aluminum in solution.

In another method of operation, the mixture of beryllium and aluminum carbides produced' in the rst stage'of the treatment may be digested under heat and autogenous pressure with caustic liquor. In these circumstances, the alu-- minum content of the starting material is solubilized while the beryllium is precipitated under pressure in the strong caustic. After separation of the illtrate, the caustic liquor can be recycled and reused in the process.

It is particularly to be observed that the present type of process is available for employment with acids other than sulphuric. Thus, in lieu of the sulphuric acid pressure-digestion described above, hydrouoric acid may be utilized. Similarly, acids, such as hydrochloric, 4phosphoric acid andithe like, may be employed. The cake produced by such digestion may be leached to separate the soluble beryllium and iron iiuorides from the substantially ,insolublealum'inum fluoride. The liltrate, that is to say, the beryllium and iron uoride solution may then be treated this point that where ysuch with a suitable agent to precipitate the beryllium and iron values. In this type ofY hydrofluoric digestion also, nickel or other metal may be added to the mass which is to undergo'digestion in the form of a suitable salt and recovered in admixture with the beryllium and iron.

Again, infcarrying out the process, acid salts of the metals to be recovered may be utilized in conjunction with acid, for example, acid salts of ain oxyuoride. V

. over -are obtained.

s the iron to the trivalent state.

duced from the ore, may be digested with caustic to produce a solution containing soluble aluminum hydroxide. This solution may be filtered to remove the beryllium and carbon and the filtrate may then be diluted and reacted with sulphuric acid to recover alum and sodium sulphate.

The compounds of beryllium in mixture with other metal values produced according to these methods may be used directly for the production of master alloys. For example, according to the methods described, a master addition agent o r alloy comprised of beryllium, iron and nickel, may be produced for such purpose by suitably reducing a mixture of beryllium hydroxide, iron oxide, nickel oxide and carbon, or by employing the carbides of beryllium and aluminum instead of the carbon. This master alloy will carry a high percentage of beryllium. Such master alloy may be shipped as a separate commodity to steel plants Ato be there added to iron melts to produce an ultimate alloy of the desired composition.

In another method of procedure, the beryllium ore may rst be treated with nominal amounts of alkali, as described in my Patent 1,991,269.` To this fused mass may then be added salts of the metals desired, such for example, as nickel sulphate, or copper sulphate (if a beryllium alloy is desired), together with a sufficient amount of strong sulphuric acid to dissolve all the aluminum and beryllium in the fused mass. Such digestion may be eiected under heat and under the autogenous pressures developed, and in ordinary circumstances, temperature of the order of 100 C. to 500 C. or more, and pressures of from 10 pounds to several hundred pounds per square inch, are utilized. As in the other processes described, the resulting digested product may be leached to segregate the soluble metal Values from the insoluble ones. Again, this process, that is to say, the process of preliminarily fusing the ore with alkali, may be employed with a fluoride digestion in which case the aluminum, which is in form of the insoluble fluoride, may be separated directly from the other metal values. The product so produced may then be employed to produce master alloys for addition agents in suitable metallurgical melts and reducing them so as to be alioyed with the melt. f

Still another method of producing beryllium available for reduction to the alloys is to decompose the powdered beryl with sodium silicofluoride under heat and pressure using for example approximately 60 lparts by weight of beryl to 40 parts, more or Such digestion may be carried out at a temperature of500 C. and at pressures of from 25 to 100 or more" pounds. The resulting cake may be leached with water to recover the iron and beryllium as nuorides in the water solution, leaving the aluminum 'as an insoluble salt. With this type of process,

this particular type of process, dining agent like hydrogen peroxide, or equivalent, may be added to the'leach liquor to convert tion carrying the iron beryllium uorldes (together, if desired, with nickel) may then be treated to precipitate the metal values by adding a suitable alkali, like soda ash, or ammonia. During.

this step, reducing agents such' as carbon or carbides may be added 'to the solution'or'to the precipitate so as to produce a mass'which, after compacting or briquetting, may be added to a suitable extractions of 90 per cent. and' It will be appreciated that in' if desired, an oxi` less, by weight of the fluoride. I

4The aqueous soluferrous melt to produce a beryllium-containing master alloy.

As will be appreciated, it is possible, by the several processes described, to produce a precipitate or concentrate comprised of beryllium and iron oxides, or hydroxides, together with other reducible metal oxides such as nickel or other valuable alloying metals. Such a composite, presents an excellent material for addition to ferrous melts for the production of the master alloy of iron-beryllium. For this purpose. it is desirable to briquette this mixture so as to produce a dense mass. Preferably also during the briquetting operation a slagging material should be added. It is found that avery suitable material for this purpose is a calcium and/or magnesium cement and a slagging material having the characterisincorporated in the briquette, it is advisable to add such material to the melt so as to insure the presence of a reducing slag. Obviously, combination of the two may be utilized, that is to say, a reducing Aslag material may be incorporated in the beryllium concentrate and additional quantities of the reducing slag may be sprinkled on the top of the melt during reduction. Wh'en the production of the alloy is carried out in a closed furnace, the hydrocarbon gases produced in the earlier stages of the process may be utilized as a reducing agent.

The processes described hereinbefore relate particularly to the ultimate production of iron beryllium alloys and for this purpose methods have been described for eliminating the aluminum contained in the ore from the ultimate addition agent. It will be understood that the present methods are available 'for the production of master alloys or addition agents to be utilized in the production of non-ferrous beryllium alloys. In th'ese circumstances, as will be appreciated, the ultimate concentrate may include the beryllium and aluminum content of the ore, or the beryllium content alone in the formof oxides or hydroxides, from which the iron has been removed.

It will also be described herein may be invoked for theV production of concentrates available the production of beryllium-nickel alloys.

In this particular case, it is to be observed that when beryllium and nickel are combined to form an alloy, an exothermic reaction takes place. Under the concept of the present invention, as explained, beryllium-nickel alloys may 'be produced by reducing a mixture of beryllium oxide and nickel oxide. -The beryllium oxide may be prepared by converting the beryl ore as above described, then digesting the converted product, adding a suitable nickel salt such as nickel sulphate in the digest, recovering the beryllium and nickel together by leaching the digest and recovering the two metal Avalues as hydroxides or oxides. These mixed hydroxides or oxides may then be reduced by means of carbon or better by means of beryllium aluminum carbides heretofore described.

In these circumstances, bygreducing this beryllium nickel hydroxide or oxide mixture, the exothermic heat is developed which greatly facilitates the reduction and alloying fof the two metals. Cobalt also may be alioyed in the same manner or nickel and cobalt together, with berylunderstood that the methodsfor employment in I treating beryl to convert the lium and the same exothermic heat wili form to 4facilitate the reduction to the binary or ternary alloys. 'f

:imams these are given to exemplify the underlying principles involved, and not as necessarily limiting the invention to the methods mentioned.

In the accompanying drawing is shown a diagrammatic flow sheet of the process.

I claim: l

l. A method of producing beryllium-containing metallurgical-concentrates which comprises,

beryllium and aiuminum contents to the corresponding carbides, substantially fre'e fromsilica, heating the' carbides under heat and pressure in the presence of sluphur-ic acid to' form the corresponding sulphates; leaching the digest and then treating the leached material to segregate compounds. I

2. method of producing beryllium-contain particular compounds or ing metallurgical concentrates which comprises,

'treating beryl to convert the iron beryllium and aluminum contents to the corresponding carbides, substantially free from silica, digesting the carbide mass under heat and pressure in the presence o! sulphuric acid, leaching the digest cake and treating-the leach with caustic; illtering the solution so as to separate the insoluble compounds of iron and beryllium from the solu- -ble aluminumcompounds.

3. A method of producing beryllium-containing metallurgical concentrates for the production of alloys which comprises, treating beryl to 20' the desired metal I convert the beryllium and aluminum contents to. the corresponding carbides, substantially free from silica, adding to the carbide mass a compound of a metal desired in the'ultimate alloy: digesting the mass under heat and pressure with a mineral acid, recovering from the digestthe beryllium content, together' with the -sid metal value and utilizing the beryllium and such metal,

values for-the production of an alloy.-

HARRY HOWARD ARMSTRONG. 

